Ambient-temperature molten salts and process for producing the same

ABSTRACT

Ambient-temperature molten salts of formula (I): 
                         
wherein Y +  is a cation selected from the group consisting of an ammonium ion, a sulfonium ion, a pyridinium ion, a(n) (iso)thiazolium ion, and a(n) (iso)oxazolium ion that may be optionally substituted with C 1-10  alkyl and/or C 1-10  alkyl having ether linkage, provided that the above cation has at least one substituent of —CH 2 Rf 1  or —OCH 2 Rf 1  (wherein Rf 1  is C 1-10  perfluoroalkyl); Rf 2  and Rf 3  are independently C 1-10  perfluoroalkyl or may together form C 1-4  perfluoroalkylene; and X is —SO 2 — or —CO—.

This is a division of U.S. patent application Ser. No. 10/979,220, filedNov. 3, 2004 now U.S. Pat. No. 7,534,509, which is incorporated hereinby reference in its entirety.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of U.S. patent application Ser. No. 10/979,220, filedNov. 3, 2004, which is herein incorporated by reference in its entirety.

TECHNICAL FIELD

The present invention relates to a compound that is used for producinghydrophobic, highly conductive ambient-temperature molten salts, ionicliquids, or the like that are useful in the field of material science.More particularly, the present invention relates to a novel compoundwhich enables fluoroalkyl and imide anion to be introducedsimultaneously and a method for producing the same. Further, the presentinvention relates to novel ambient-temperature molten salts having widepotential windows and high ion conductivities and a method for producingthe same.

BACKGROUND ART

A compound comprising 1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumcation and —N(SO₂CF₃)₂ imide anion is known to have fluoroalkyl andimide anion. This compound is useful as hydrophobic, highly conductiveambient-temperature molten salts (Inorganic Chemistry, vol. 35, pp.1168-1178 (1996)).

A method for producing such 1-methyl-3-(fluoroalkyl)imidazolium imide isknown. In this method, fluoroalcohol is allowed to react withtrifluoromethanesulfonic anhydride, the reaction product is then allowedto react with 1-methylimidazole to obtain1-methyl-3-(fluoroalkyl)imidazolium trifluoromethanesulfonate, and theresultant is allowed to react with lithium imide salt to obtain1-methyl-3-(fluoroalkyl)imidazolium imide by salt exchange (InorganicChemistry, vol. 35, pp. 1168-1178 (1996)). This conventional method,however, was seriously deficient from the viewpoints of yield, which wasas low as 15% as the total yield from 1-methylimidazole, and difficultyin obtaining a highly purified product.

It was reported that (2,2,2-trifluoroethyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl)imide had been synthesized and this couldbe used as an agent for introducing trifluoroethyl (ChemicalCommunication, 1998, pp. 2241-2242). However,(2,2,2-trifluoroethyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl)imide had low crystallinity, and thus,isolation or purification thereof was disadvantageously complicated.

In the production of (2,2,2-trifluoroethyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl)imide, there was only one known suitablereaction solvent, i.e., 1,1,2-trichlorotrifluoroethane (CFC-113)(Chemical Communication, 1998, pp. 2241-2242). CFC-113, however, was anozone depleting substance and had caused severe environmentaldestruction. Thus, industrialization thereof was difficult.

Although fluoroalkylaryliodonium sulfonate is known (Bulletin of theChemical Society of Japan, vol. 60, pp. 3307-3313 (1987) and U.S. Pat.No. 4,873,027 (JP Patent Publication (Kokoku) No. 3-58332 B (1991)),fluoroalkyl and imide anion cannot be simultaneously introduced with theuse of this compound.

As described above, there was no method that could simultaneously andefficiently introduce fluoroalkyl and imide anion.

Recently, triazolium imide salt having Rf′CH₂CH₂— (wherein Rf¹ is C₁₋₆perfluoroalkyl) has been reported as an ambient-temperature molten salt(Journal of Organic Chemistry, Vol. 67. pp. 9340-9345(2002)). However,triazole compound as a starting material is expensive and it requires atleast three reaction steps.

Further, ammonium imide salt having Rf″CH₂CH₂— (wherein Rf″ is C₄₋₁₀perfluoroalkyl) has been reported (Tetrahedron Letters, Vol. 44. pp.9367-9370(2003)). However, it requires two reaction steps to synthesizethe ammonium imide salt having Rf″CH₂CH₂—.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the ion conductivity of an imidazolium molten salt.

DISCLOSURE OF THE INVENTION

Objects of the present invention are to provide a compound that enablesfluoroalkyl and imide anion to be simultaneously and highly efficientlyintroduced, a method for easily producing ambient-temperature moltensalts with high yield using the aforementioned compound, and novelambient-temperature molten salts having wide potential windows and highion conductivities.

The present inventors have conducted concentrated studies in order toovercome the aforementioned drawbacks. As a result, they have found thatfluoroalkyl and imide anion can be easily, simultaneously, and highlyefficiently introduced in a single step with the use of afluoroalkylaryliodonium imide compound. This has led to the completionof the present invention.

More specifically, the present invention includes the followinginventions.

(1) Ambient-temperature molten salts of formula (I):

wherein,Y⁺ is a cation selected from the group consisting of an ammonium ion, asulfonium ion, a pyridinium ion, a(n) (iso)thiazolium ion, and/or a(n)(iso)oxazolium ion, which may be optionally substituted with C₁₋₁₀ alkyland/or C₁₋₁₀ alkyl having ether linkage, provided that said cation hasat least one substituent of —CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl);Rf² and Rf³ are independently C₁₋₁₀ perfluoroalkyl or may together formC₁₋₄ perfluoroalkylene; and,X is —SO₂— or —CO—.

(2) The ambient-temperature molten salts according to (1) above, whereinY⁺ is an ammonium ion of formula (II):

wherein R¹ to R⁴ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, —CH₂Rf¹, or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl) or two of R¹ to R⁴ may together form a morpholine,piperidine, or pyrrolidine ring, provided that at least one of R¹ to R⁴is —CH₂Rf¹ or —OCH₂Rf¹.

(3) The ambient-temperature molten salts according to (1) above, whereinY⁺ is a sulfonium ion of formula (III):

wherein R¹ to R³ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl), provided that at least one of R¹ to R³ is —CH₂Rf¹.

(4) The ambient-temperature molten salts according to (1) above, whereinY⁺ is a pyridinium ion of formula (IV):

wherein R¹ to R⁵ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, —CH₂Rf¹, or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl), and R⁶ is —CH₂Rf¹ or OCH₂Rf¹.

(5) The ambient-temperature molten salts according to (1) above, whereinY⁺ is a(n) (iso)thiazolium ion or (iso)oxazolium ion of formula (V):

wherein R¹ to R³ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl), R⁴ is —CH₂Rf¹, and Z is an oxygen or sulfur atom.

(6) Ambient-temperature molten salts of formula (VI):

wherein R¹ to R⁵ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl), provided that at least one of R³ or R⁵ is —CH₂Rf¹, Rf²and Rf³ are independently C₁₋₁₀ perfluoroalkyl or may together form C₁₋₄perfluoroalkylene.

(7) A fluoroalkylfluorophenyliodonium imide compound of formula (VII):

wherein Rf¹ is C₁₋₁₀ perfluoroalkyl, Rf² and Rf³ are independently C₁₋₁₀perfluoroalkyl or together form C₁₋₄ perfluoroalkylene.

(8) A method for producing a compound of formula (VIII):

whereinY′⁺ is a cation selected from the group consisting of an imidazoliumion, an ammonium ion, a sulfonium ion, a pyridinium ion, a(n)(iso)thiazolium ion, and a(n) (iso)oxazolium ion, which may beoptionally substituted with C₁₋₁₀ alkyl and/or C₁₋₁₀ alkyl having etherlinkage, provided that said cation has at least one substituent of—CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀ perfluoroalkyl); and,Rf² and Rf³ are independently, C₁₋₁₀ perfluoroalkyl or may together formC₁₋₄ perfluoroalkylene,which comprises reacting a heteroatom-containing compound selected fromthe group consisting of imidazole, amine, amine N-oxide, sulfide,pyridine, pyridine N-oxide, (iso)thiazole, and (iso)oxazole, which maybe optionally substituted with C₁₋₁₀ alkyl, C₁₋₁₀ alkyl having etherlinkage, —CH₂Rf¹ and/or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀ perfluoroalkyl),with a fluoroalkylaryliodonium imide compound of formula (IX):

wherein Rf¹, Rf², and Rf³ are as defined above, and Ar is unsubstitutedphenyl or phenyl that may be optionally substituted with halogen atom orC₁₋₁₀ alkyl, to give a compound of formula (VIII).

(9) The production method according to (8) above, wherein —Ar is phenylor represented by the following formula:

(10) The production method according to (8) above, wherein —Ar isrepresented by the following formula:

The present invention is hereafter described in detail.

The term “C₁₋₁₀ alkyl” used herein refers to a straight-chain orbranched alkyl group having 1 to 10 carbon atoms. Examples thereofinclude methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

The term “C₁₋₁₀ perfluoroalkyl” used herein refers to an alkyl group asdefined above in which all hydrogen atoms are substituted with fluorineatoms. Examples thereof include, for example, CF₃—, CF₃CF₂—, CF₃(CF₂)₂—,CF₃(CF₂)₃—, CF₃(CF₂)₄—, CF₃(CF₂)₅—, CF₃(CF₂)₆—, CF₃(CF₂)₇—, CF₃(CF₂)₈—,CF₃(CF₂)₉—, (CF₃)₂CF—, and (CF₃CF₂)(CF₃)CF—, (CF₃)₂CFCF₂—,(CF₃)₂CFCF₂CF₂—.

Ambient-temperature molten salts compound of formula (I) according tothe present invention is now described:

wherein Y⁺ is a cation selected from a group consisting of ammonium ion,sulfonium ion, pyridinium ion, (iso)thiazolium ion and (iso)oxazoliumion, which may be optionally substituted with C₁₋₁₀ alkyl and/or C₁₋₁₀alkyl having ether linkage, provided that said cation has at least onesubstituent of —CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀perfluoroalkyl); Rf² and Rf³ are independently C₁₋₁₀ perfluoroalkyl ormay together form C₁₋₄ perfluoroalkylene; and X is —SO₂— or —CO—.

Rf¹ is C₁₋₁₀ perfluoroalkyl, more preferably C₁₋₇ perfluoroalkyl, andfurther preferably C₁₋₄ perfluoroalkyl.

Rf² and Rf³ may independently be any combinations of C₁₋₁₀perfluoroalkyls as exemplified above. More preferably, Rf² and Rf³ areindependently combinations of perfluoroalkyls, such as ⁻N(SO₂CF₃)₂,⁻N(SO₂CF₃)(SO₂C₂F₅), ⁻N(SO₂C₂F₅)₂, ⁻N(SO₂C₃F₇)₂, ⁻N(SO₂C₄F₉)₂,⁻N(SO₂CF₃) (SO₂C₄F₉), ⁻N(SO₂CF₃)(SO₂C₆F₁₃), ⁻N(SO₂CF₃)(SO₂C₈F₁₇), or⁻N(SO₂C₄F₉)(SO₂C₆F₁₃).

Furthermore, Rf² and Rf³ may independently be any combinations of C₁₋₇perfluoroalkyls, more preferably C₁₋₄ perfluoroalkyls.

Alternatively, Rf² and Rf³ may together form C₁₋₄ perfluoroalkylene. Insuch a case, an imide anion portion forms a cyclic structure as shownbelow.

An example of C₁₋₄ perfluoroalkylene is straight chain or branched C₁-C₄perfluoroalkylene. —CF₂—, —CF₂CF₂—, —CF(CF₃)CF₂—, —CF₂CF₂CF₂—,—CF₂CF₂CF₂CF₂—, or the like is preferable.

Examples of a cation of a hetero atom-containing compound represented byY⁺, which may be optionally substituted with C₁₋₁₀ alkyl and/or C₁₋₁₀alkyl having ether linkage, include cations derived from amine, amineN-oxide, sulfide, pyridine, pyridine N-oxide, (iso)thiazole, and(iso)oxazole. Specific examples are ammonium ion, sulfonium ion,pyridinium ion, (iso)thiazolium ion, and (iso)oxazolium ion. It shouldbe noted that these cations have at least one substituent of —CH₂Rf¹ or—OCH₂Rf¹ (wherein Rf¹ is C₁₋₁₀, preferably C₁₋₇, and more preferablyC₁₋₄ perfluoroalkyl).

Y⁺ is preferably a cation selected from the following:

an ammonium ion of formula (II):

wherein R¹ to R⁴ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, —CH₂Rf¹, or —OCH₂Rf¹ (wherein Rf¹ is asdefined above) or two of R¹ to R⁴ may together form a morpholine,piperidine, or pyrrolidine ring, provided that at least one of R¹ to R⁴is —CH₂Rf¹ or —OCH₂Rf¹;

a sulfonium ion of formula (III):

wherein R¹ to R³ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is as definedabove), provided that at least one of R¹ to R³ is —CH₂Rf¹;

a pyridinium ion of formula (IV):

wherein R¹ to R⁵ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, —CH₂Rf¹, or —OCH₂Rf¹ (wherein Rf¹ is asdefined above), and R⁶ is —CH₂Rf¹ or OCH₂Rf¹; and

a(n) (iso)thiazolium ion or (iso)oxazolium ion of formula (V):

wherein R¹ to R³ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is as definedabove), R⁴ is —CH₂Rf¹, and Z is an oxygen or sulfur atom.

An anion portion in a compound of formula (I) preferably has anasymmetric structure. In other words, —SO₂Rf² and —XRf³ are preferablynot identical to each other.

Furthermore, the present invention includes the ambient-temperaturemolten salts of formula (VI):

wherein R¹ to R⁵ are independently hydrogen atom, C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, or —CH₂Rf¹ (wherein Rf¹ is C₁₋₁₀, preferablyC₁₋₇, and more preferably C₁₋₄ perfluoroalkyl), provided that at leastone of R³ or R⁵ is —CH₂Rf¹, Rf² and Rf³ are independently C₁₋₁₀,preferably C₁₋₇, and more preferably C₁₋₄ perfluoroalkyl or may togetherform C₁₋₄ perfluoroalkylene.

The melting point of the ambient-temperature molten salts of formulae(I) and (VI) is low, and is generally ambient temperature or lower.“Ambient-temperature” refers to temperature under circumstances withoutany special heating and cooling and is, for example, about 25° C. Eventhough a salt has a melting point of ambient temperature or higher(e.g., about 100° C.), it may exist in a liquid state (a supercooledliquid) at ambient temperature due to the supercooling phenomenon. Theterm “ambient-temperature molten salts” used herein refers to not onlysalts having a melting point of ambient temperature or lower but alsosalts that can exist in a liquid state (a supercooled liquid) at ambienttemperature or lower even though its melting point is ambienttemperature or higher.

The ambient-temperature molten salts of formulae (I) and (VI) have highconductivities, wide potential windows, incombustibility, andnonvolatile properties. Thus, they are useful compounds for electrolytesfor lithium cells or the like.

A method for producing the ambient-temperature molten salts of formula(I′) is then described:

wherein Y′⁺, Rf², Rf³, and X are as defined above.

The ambient-temperature molten salt compound of formula (I′) wherein Xis —SO₂— can be produced by allowing a compound of formula (IX):

(wherein Ar is unsubstituted phenyl or phenyl that may be optionallysubstituted with halogen atom or C₁₋₁₀ alkyl, and Rf¹, Rf², and Rf³ areas defined above) to react with a hetero atom-containing compoundselected from a group consisting of imidazole, amine, amine N-oxide,sulfide, pyridine, pyridine N-oxide, (iso)thiazole and (iso)oxazole.

Ar denotes substituted or unsubstituted phenyl. When it is substitutedphenyl, examples of substituents include halogen atom and C₁₋₁₀ alkyl.Examples of halogen atom include fluorine, chlorine, bromine, and iodineatom, with fluorine atom being preferable. An example of C₁₋₁₀ alkyl isthe aforementioned alkyl, and it is preferably C₁₋₄ alkyl such asmethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.Unsubstituted phenyl and fluorophenyl are particularly preferable fromthe viewpoints of reaction efficiency, yield, and stability.Fluorophenyl is more preferable from the viewpoints of easy isolationand purification in the production process of the starting compound offormula (IX) and simultaneous production of useful fluoroiodobenzene asdescribed later.

Hetero atom-containing compounds may be substituted with C₁₋₁₀ alkyl,C₁₋₁₀ alkyl having ether linkage, —CH₂Rf¹, and/or —OCH₂Rf¹ (wherein Rf¹is as defined above). The term “C₁₋₁₀ alkyl having ether linkage” usedherein refers to “C₁₋₁₀ alkyl” as defined above, which contains at leastone ether linkage (—O—) in its alkyl chain. Examples thereof includeCH₃O—, CH₃OCH₂—, CH₃O(CH₂)₂—, CH₃CH₂OCH₂—, CH₃CH₂OCH₂CH₂—, CH₃O(CH₂)₃—,CH₃CH₂O(CH₂)₃—, and CH₃O(CH₂)₂O(CH₂)₂O—. Such alkyl having ether linkagemay be substituted with fluorine atom (e.g. CF₃CH₂OCH₂CH₂—).

Hetero atom-containing compounds as used herein are commerciallyavailable or may be prepared by known method. The hetero atom-containingcompounds having —CH₂Rf¹ or —OCH₂Rf¹ substituent may be prepared, forexample, by employing Rf¹CH₂I⁺(Ph)TfO⁻(TfO⁻: trifluoromethanesulfonateanion) as introducing agent for —CH₂Rf¹ (see, Journal of FluorineChemistry, 31, pp. 231-236(1986)).

In the reaction between the compound of formula (IX) and a heteroatom-containing compound, the amount of the hetero atom-containingcompound to be used is generally between 0.2 moles and 2 moles relativeto 1 mole of the compound of formula (IX). It is preferably between 0.3and 1.5 moles from the viewpoints of economical efficiency and yield.

The compound of formula (IX) is generally allowed to react with a heteroatom-containing compound in a solvent. When the hetero atom-containingcompound is liquid, the reaction can be carried out without the use of asolvent. Examples of a solvent that is used in the aforementionedreaction include: chloroalkanes, such as methylene chloride, chloroform,carbon tetrachloride, dichloroethane, trichloroethane, ortetrachloroethane; fluorochloroalkanes, such astrichlorotrifluoroethane; aromatic compounds, such as benzene,chlorobenzene, fluorobenzene, or toluene; ethers, such as diethyl ether,dipropyl ether, diisopropyl ether, tetrahydrofuran, or dioxane;nitrites, such as acetonitrile or propionitrile; nitro compounds, suchas nitromethane, nitroethane, or nitrobenzene; water; alcohols, such asmethanol, ethanol, propanol, isopropanol, butanol, sec-butanol, ort-butanol; and mixtures thereof. Among these solvents, use of carbontetrachloride or fluorochloroalkane is preferably refrained from theenvironmental problem of ozone depletion.

The reaction temperature varies depending on reactivity of a heteroatom-containing compound to be used. It is generally between −80° C. and+100° C., and it is preferably between −50° C. and +80° C. in order toproceed the reaction with high yield and efficiency.

A compound of formula (VII):

(wherein Rf¹, Rf² and Rf³ are as defined above) that is used in theabove production method is novel.

When a compound of formula (VII) is used as starting material forpreparing an ambient-temperature molten salt of formula (I′),fluoroiodobenzene is produced together. Fluoroiodobenzene is animportant intermediate for producing medicines or agrochemicals (see CA85-108420f). Thus, a compound of formula (VII) according to the presentinvention is a useful not only for introducing fluoroalkyl Rf¹CH₂— (Rf¹is as defined above) easily together with imide anionN⁻(SO₂Rf²)(SO₂Rf³)(Rf² and Rf³ are as defined above) in one reactionstep, but also for producing fluoroiodobenzene, which is important asmedicinal and agrochemical intermediate, in good yield.

Negative charge in the anion portion of the compound of formulae (IX)and (VII) is not localized in a nitrogen atom. The anion portion has aresonance structure as shown below.

The fluoroalkylaryliodonium imide compound of formula (IX) according tothe present invention can be produced in the following manner.

The compound of formula (IX) can be produced by allowing a fluoroalkyliodoso compound of formula (X):Rf¹CH₂I(OCORf⁴)₂  (X)(wherein Rf¹ is as defined above and Rf is C₁₋₄ perfluoroalkyl) to reactwith Ar—H (wherein Ar is as defined above) and with an imide compound offormula (XI):

(wherein Rf² and Rf³ are as defined above).

In formula (X), Rf⁴ is C₁₋₄ perfluoroalkyl, and examples thereof includeCF₃—, CF₃CF₂—, CF₃(CF₂)₂—, (CF₃)₂CF—, CF₃(CF₂)₃—, (CF₃CF₂)(CF₃)CF—,(CF₃)₂CFCF₂—, and (CF₃)₃C—.

The iodoso compound of formula (X) can be produced from commerciallyavailable iodofluoroalkane by a conventional technique. For example, itcan be easily produced by allowing iodofluoroalkane: Rf¹CH₂I (whereinRf¹ is as defined above) to react with perfluoroalkyl peroxy carboxylicacid: Rf⁴COOOH (wherein Rf⁴ is as defined above) (for example, Bulletinof the chemical Society of Japan, vol. 60, pp. 3307-3313 (1987)). Forexample, perfluoroalkyl peroxy carboxylic acid: Rf⁴COOOH can be easilyproduced by allowing a 20% to 60% hydrogen peroxide solution to reactwith perfluoroalkyl carboxylic anhydride: (Rf⁴CO)₂O in the presence ofperfluoroalkyl carboxylic acid: Rf⁴COOH.

Alternatively, the iodoso compound of formula (X) can be obtained bychlorinating iodofluoroalkane: Rf¹CH₂I (wherein Rf¹ is as defined above)using chlorine gas and then processing it with silver salt ofperfluoroalkyl carboxylic acid (Tetrahedron Letters, vol. 35 (No. 43),pp. 8015-8018 (1994)).

Examples of iodoso compounds of formula (X) that are used in thisreaction include CF₃CH₂I(OCOCF₃)₂, CF₃CH₂I(OCOC₂F₅)₂, CF₃CH₂I(OCOC₃F₇)₂,CF₃CH₂I(OCOC₄F₉)₂, CF₃CF₂CH₂I(OCOCF₃)₂, CF₃(CF₂)₂CH₂I(OCOCF₃)₂,CF₃(CF₂)₃CH₂I(OCOCF₃)₂, CF(CF₂)₄CH₂I(OCOCF₃)₂, CF₃(CF₂)₈CH₂I(OCOCF₃)₂,CF₃(CF₂)₆CH₂I(OCOCF₃)₂, CF₃(CF₂)₇CH₂I(OCOCF₃)₂, CF₃(CF₂)₈CH₂I(OCOCF₃)₂,CF₃(CF₂)₉CH₂I(OCOCF₃)₂, (CF₃)₂CFCH₂I(OCOCF₃)₂,(CF₃CF₂)(CF₃)CFCH₂I(OCOCF₃)₂, (CF₃)₂CFCF₂CH₂I(OCOCF₃)₂, and(CF₃)₂CFCF₂CF₂CH₂I(OCOCF₃)₂, CF₃CH₂I(OCOCF₃)₂, CF₃CF₂CH₂I(OCOCF₃)₂,CF₃(CF₂)₂CH₂I(OCOCF₃)₂, CF₃(CF₂)₃CH₂I(OCOCF₃)₂, CF₃(CF₂)₄CH₂I(OCOCF₃)₂,CF₃(CF₂)₅CH₂I(OCOCF₃)₂, CF₃(CF₂)₆CH₂I(OCOCF₃)₂, CF₃(CF₂)₇CH₂I(OCOCF₃)₂,CF₃(CF₂)₈CH₂I(OCOCF₃)₂, CF₃(CF₂)₉CH₂I(OCOCF₃)₂, (CF₃)₂CFCH₂I(OCOCF₃)₂,(CF₃)₂CFCF₂CH₂I(OCOCF₃)₂, (CF₃)₂CFCF₂CF₂CH₂I(OCOCF₃)₂, and the like arepreferable.

A starting material, unsubstituted benzene or benzene Ar—H that may beoptionally substituted with halogen atom or C₁₋₁₀ alkyl, is commerciallyavailable.

Imide of formula (XI) is commercially available or can be easilyproduced by conventional techniques (for example, Inorganic Chemistry,vol. 23, pp. 3720-3723 (1984); Chem. Ztg., vol. 96, p. 582 (1972); andJP Patent Publication (Kokai) No. 62-26264 A (1987)).

The stoichiometric ratios of an iodoso compound (X), a benzene compoundAr—H, and an imide compound (XI) that are used as starting materials areas follows.

The amount of Ar—H to be used is generally 0.8 to 10 moles relative to 1mole of the iodoso compound of formula (X), and it is preferably 0.9 to2 moles from the viewpoints of economical efficiency and yield. Theamount of the imide compound of formula (XI) to be used is generally 0.7to 2 moles relative to 1 mole of the iodoso compound of formula (X), andit is preferably 0.8 to 1.5 moles, and more preferably 0.9 to 1.2 molesfrom the viewpoints of economical efficiency and yield.

The aforementioned starting material is allowed to react in a solvent attemperature from −90° C. to +50° C., and preferably from −30° C. to roomtemperature.

Examples of solvents include: chloroalkanes, such as methylene chloride,chloroform, carbon tetrachloride, dichloroethane, and trichloroethane;fluorochloroalkanes, such as trichlorofluoromethane,trichlorofluoroethane, and trichlorotrifluoroethane; halogenated fattyacids, such as trifluoroacetic acid, chlorodifluoroacetic acid,pentafluoropropionic acid, and heptafluorobutyric acid; halogenatedfatty acid anhydrides, such as trifluoroacetic anhydride,chlorodifluoroacetic anhydride, pentafluoropropionic anhydride, andheptafluorobutyric anhydride; and mixtures thereof. Chloroalkanes orfluorochloroalkanes are preferable in terms of simple handleability. Inorder to avoid the environmental problem of ozone depletion,chloroalkanes excluding carbon tetrachloride are particularlypreferable. Further, methylene chloride is most preferable from theviewpoints of yield, efficiency, and recovery that is necessary foravoiding the environmental problem.

The amount of a solvent to be used is generally 100 litters or smaller,and preferably 10 liters or smaller, relative to 1 mole of thefluoroalkyl iodoso compound of formula (X). It is particularlypreferably 5 litters or smaller from the viewpoint of economicalefficiency. The minimal amount of a solvent is not particularly limited,and the amount, with which the reaction efficiently proceeds, isadequately selected.

The reaction period may be adequately determined depending on a startingmaterial, a solvent, reaction temperature, or the like to be employed.It is generally between 5 minutes and 60 hours, and preferably between30 minutes and 30 hours.

After the completion of the reaction, the reaction product is subjectedto general post-treatment and then purified by a technique known topersons skilled in the art, such as recrystallization, to obtain asubject compound of formula (IX).

A compound of formula (IX) wherein Ar is fluorophenyl is afluoroalkylfluorophenyliodonium imide compound of formula (VII), whichis produced by using fluorobenzene as Ar—H. Afluoroalkylfluorophenyliodonium imide compound of formula (VII) hasparticularly high crystallinity, and it can be easily isolated andpurified by recrystallization. For example, while the melting point of(2,2,2-trifluoroethyl)(phenyl)iodonium imide is between 76° C. and 78°C. (see Example 7), that of(2,2,2-trifluoroethyl)(p-fluorophenyl)iodonium imide is high, i.e.,between 98.5° C. and 100° C. (see Example 1).(2,2,3,3,3-Pentafluoropropyl)(phenyl)iodonium imide is an oily amorphoussubstance at room temperature (see Example 8). In contrast, the meltingpoint of (2,2,3,3,3-pentafluoropropyl)(p-fluorophenyl)iodonium imide issurprisingly a crystalline substance having a high melting point between91° C. and 93° C. (see Example 3).

A compound (I) wherein X is —CO— or —SO₂— and a compound (VI) can beproduced by salt exchange. Salt exchange is a known technique and can becarried out in accordance with the method described in, for example,Inorganic Chemistry, vol. 35, pp. 1168-1178 (1996) or Journal ofPhysical Chemistry, B, vol. 102, pp. 8858-8864 (1998).

When a compound is produced by salt exchange, a salt selected from thegroup consisting of imidazolium salt, ammonium salt, sulfonium salt,pyridinium salt, (iso)thiazolium salt, and (iso)oxazolium salt that maybe optionally substituted with C₁₋₁₀ alkyl and/or C₁₋₁₀ alkyl havingether linkage, provided that the above cation has at least onesubstituent of —CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is as defined above) isallowed to react with a salt of formula (XII):

(wherein Rf² and Rf³ are as defined above, X is —CO— or —SO₂—, and M⁺ isa monovalent metal ion, such as Li⁺, Na⁺, or K⁺).

Preferable examples of imidazolium salt, ammonium salt, sulfonium salt,pyridinium salt, (iso)thiazolium salt, and (iso)oxazolium salt that hasat least one substituent of —CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is asdefined above) and may be optionally substituted with C₁₋₁₀ alkyl and/orC₁₋₁₀ alkyl having ether linkage include salts of a cation representedby Y′⁺ as mentioned above (e.g., an imidazolium, ammonium, sulfonium,pyridinium, (iso)thiazolium, or (iso)oxazolium ion) with an anion (e.g.,trifluoromethanesulfonate anion, TfO⁻). These salts can be produced byconventional techniques. For example, R^(a)R^(b)R^(c)N⁺CH₂Rf¹·TfO⁻(wherein R^(a), R^(b), and R^(c) are independently C₁₋₁₀ alkyl, C₁₋₁₀alkyl having ether linkage, —CH₂Rf¹ or —OCH₂Rf¹ (wherein Rf¹ is asdefined above)) can be produced by allowing amine R^(a)R^(b)R^(c)N toreact with Rf¹CH₂I⁺(Ph)TfO⁻ (Bulletin of the Chemical Society of Japan,vol. 64, pp. 2008-2010 (1991)).

Salt exchange between the aforementioned salt and the salt of formula(XII) can exchange salt anion with imide anion N⁻(SO₂Rf²)(XRf³) (whereinRf², Rf³, and X are as defined above). Thus, a compound of formula (I)or (VI) can be obtained.

BEST MODES FOR CARRYING OUT THE INVENTION

The present invention is hereafter described in more detail withreference to the following examples, although the scope of the presentinvention is not limited to these examples.

Example 1 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 1)

CF₃CH₂I(OCOCF₃)₂ (43.6 g, 100 mmol), HN(SO₂CF₃)₂ (28.1 g. 100 mmol), anddried methylene chloride (125 ml) were placed in a reaction vessel, thecontent of the reaction vessel was subjected to nitrogen substitution,and the mixed solution was stirred at room temperature for 30 minutes.The resultant was cooled in a bath at 0° C., and fluorobenzene (14.2 ml,150 mmol) was then added dropwise thereto while stirring over the courseof 2 minutes. Thereafter, the temperature of the bath was slowly raisedto room temperature, and the mixture was allowed to react at roomtemperature for 20 hours.

After the completion of the reaction, the solvent was removed bydistillation using an evaporator at room temperature, andtrifluoroacetic acid as a side product was then removed by sucking witha vacuum pump. The obtained crystalline product was dissolved in aminimal amount of acetonitrile, and chloroform/ether was added thereto.A crystal was precipitated immediately thereafter. The precipitatedcrystal was separated by filtration, and(2,2,2-trifluoroethyl)(4-fluorophenyl)iodoniumbis(trifluoromethanesulfonyl)imide (compound 1) was obtained (yield: 47g, 80%). A sample for analysis was obtained by being recrystallized fromacetonitrile/chloroform.

Melting point: 98.5-100° C.

¹H-NMR (in CD₃CN, ppm): δ 8.15 (dd, J=6, 4 Hz, o-H), 7.35 (t, J=8 Hz,m-H), 4.75 (q, J=10 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 101.3 (t, J=10 Hz,CF₃), 84.3 (s, CF₃S), 59.9 (m, p-F)

IR (cm⁻¹): 1201 (SO₂), 1359 (SO₂)

Elemental analysis: found: C, 20.52%; H, 1.18%; N, 2.40%.

calculated: C, 20.53%; H, 1.03%; N, 2.39%.

Example 2 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 2)

Compound 2 was obtained in the same manner as in Example 1, except forthe use of CF₃CH₂I(OCOCF₃)₂ (21.8 g, 50 mmol), fluorobenzene (7.05 ml,75 mmol), and HN(SO₂CF₂CF₃)₂ (19.1 g, 50 mmol) as starting materials andCClF₂CCl₂F (100 ml) as a solvent (yield 56%).

Melting point: 79.5-80.5° C.

¹H-NMR (in CD₃CN, ppm): δ 8.15 (dd, J=9, 5 Hz, o-H), 7.36 (t, J=9 Hz,m-H), 4.76 (q, J=10 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 101.4 (t, J=10 Hz,CF₃CH₂), 84.5 (s, CF₃), 60.0 (m, p-F), 46.2 (s, CF₂S)

IR (cm⁻¹): 1215 (SO₂), 1348 (SO₂)

Elemental analysis: found: C, 20.95%; H, 1.05%; N, 2.08%.

calculated: C, 21.04%; H, 0.88%; N, 2.04%.

Example 3 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 3)

Compound 3 was obtained in the same manner as in Example 1, except forthe use of CF₃CF₂CH₂I(OCOCF₃)₂ (4.86 g, 10 mmol), fluorobenzene (1.41ml, 15 mmol), and HN(SO₂CF₃)₂ (2.81 g, 10 mmol) as starting materialsand CClF₂CCl₂F (20 ml) as a solvent (yield 72%).

Melting point: 91.0-93.0° C.

¹H-NMR (in CD₃CN, ppm): δ 8.17 (dd, J=9, 4 Hz, o-H), 7.36 (t, J=9 Hz,m-H), 4.78 (t, J=17 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 84.1 (s, CF₃S), 80.3(s, CF₃), 60.0 (m, p-F), 55.5 (t, J=17 Hz, CF₂)

IR (cm⁻¹): 1199 (SO₂), 1346 (SO₂)

Elemental analysis: found: C, 20.63%; H, 1.08%; N, 2.26%.

calculated: C, 20.80%; H, 0.95%; N, 2.21%.

Example 4 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 4)

Compound 4 was obtained in the same manner as in Example 1, except forthe use of CF₃CF₂CH₂I(OCOCF₃)₂ (9.72 g, 20 mmol), fluorobenzene (2.85ml, 30 mmol), and HN(SO₂CF₂CF₃)₂ (7.62 g, 20 mmol) as starting materialsand CH₂Cl₂ (40 ml) as a solvent (yield 62%).

Melting point: 99.3-99.8° C.

¹H-NMR (in CD₃CN, ppm): δ 8.17 (m, o-H), 7.35 (m, m-H), 4.78 (t, J=17Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 84.5 (s, CF₃CF₂S),80.5 (CF₃), 60.1 (m, p-F), 55.8 (t, J=10 Hz, CF₂), 46.2 (s, CF₂S)

IR (cm⁻¹): 1221 (SO₂), 1349 (SO₂)

Elemental analysis: found: C, 21.15%; H, 0.97%; N, 2.09%.

calculated: C, 21.24%; H, 0.82%; N, 1.91%.

Example 5 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 5)

Compound 5 was obtained in the same manner as in Example 1, except forthe use of CF₃(CF₂)₂CH₂I(OCOCF₃)₂ (5.36 g, 10 mmol), fluorobenzene (1.41ml, 15 mmol), and HN(SO₂CF₃)₂ (2.81 g, 10 mmol) as starting materialsand CH₂Cl₂ (12.5 ml) as a solvent (yield 84%).

Melting point: 58.7-59.7° C.

¹H-NMR (in CD₃CN, ppm): δ 8.19 (dd, J=9, 5 Hz o-H), 7.35 (t, J=9 Hzm-H), 4.84 (t, J=18 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 84.4 (s, SCF₃), 83.3(t, J=10 Hz, CF₃), 60.2 (m, p-F), 59.0 (m, CF₂), 38.2 (m, CF₂)

IR (cm⁻¹): 1338 (SO₂), 1203 (SO₂)

Elemental analysis: found: C, 20.82%; H, 0.86%; N, 2.18%.

calculated: C, 21.03%; H, 0.88%; N, 2.04%.

Example 6 Production of (fluoroalkyl)(fluorophenyl)iodonium imide(Compound 6)

Compound 6 was obtained in the same manner as in Example 1, except forthe use of CF₃(CF₂)₆CH₂I(OCOCF₃)₂ (7.36 g, 10 mmol), fluorobenzene (1.41ml, 15 mmol), and HN(SO₂CF₃)₂ (2.81 g, 10 mmol) as starting materialsand CH₂Cl₂ (12.5 ml) as a solvent (yield 88%).

Melting point: 67.4-68.0° C.

¹H-NMR (in CD₃CN, ppm): δ 8.20 (dd, J=9, 5 Hz o-H), 7.35 (t, J=9 Hzm-H), 4.86 (t, J=18 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 84.4 (s, SCF₃), 82.9(m, CF₃), 60.2 (m, p-F), 60.0 (m, CF₂), 42.7 (m, CF₂×2), 42.1 (m, CF₂),41.3 (m, CF₂), 37.9 (m, CF₂)

IR (cm⁻¹): 1354 (SO₂), 1204 (SO₂)

Elemental analysis: found: C, 21.65%; H, 0.69%; N, 2.01%.

calculated: C, 21.71%; H, 0.68%; N, 1.58%.

Example 7 Production of (fluoroalkyl)(phenyl)iodonium imide (Compound 7)

Reaction was conducted in the same manner as in Example 1, except forthe use of CF₃CH₂I(OCOCF₃)₂ (21.8 g, 50 mmol), benzene (6.7 ml, 75mmol), and HN(SO₂CF₃)₂ (14.1 g, 50 mmol) as starting materials andCH₂Cl₂ (62.5 ml) as a solvent.

After the completion of the reaction, methylene chloride as a solventwas removed by distillation using an evaporator at room temperature, andtrifluoroacetic acid as a side product was then removed by distillationusing a vacuum pump. Chloroform was added to the obtained oil product,and the resulting solid product was separated by filtration. This solidproduct was dissolved in acetonitrile/chloroform, the solution wasallowed to stand in a freezer (−20° C.) overnight, and the resultingcrystal was separated by filtration. Thus,(2,2,2-trifluoroethyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl)imide (compound 7) was obtained (yield:71%). A sample for analysis was obtained by recrystallization fromacetonitrile/chloroform.

Melting point: 76.0-78.0° C. (documented value (Chemical Communication,1998, pp. 2241-2242): 77-79° C.)

¹H-NMR (in CD₃CN, ppm): δ 8.13 (d, J=8 Hz o-H), 7.83 (t, J=8 Hz p-H),7.62 (t, J=8 Hz m-H), 4.76 (q, J=10 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 101.4 (t, J=10 HzCF₃), 84.2 (s, CF₃S)

IR (cm⁻¹): 1202 (SO₂), 1361 (SO₂)

Elemental analysis: found: C, 21.03%; H, 1.38%; N, 2.51%.

calculated: C, 21.18%; H, 1.24%; N, 2.47%.

Example 8 Production of (fluoroalkyl)(phenyl)iodonium imide (Compound 8)

Reaction was conducted in the same manner as in Example 1, except forthe use of CF₃CF₂CH₂I(OCOCF₃)₂ (4.86 g, 10 mmol), benzene (1.34 ml, 15mmol), and HN(SO₂CF₃)₂ (2.81 g, 10 mmol) as starting materials andCH₂Cl₂ (12.5 ml) as a solvent.

After the completion of the reaction, methylene chloride as a solventwas removed by distillation using an evaporator at room temperature, andtrifluoro acetic acid as a side product was then removed by distillationusing a vacuum pump. The oil product was dissolved in a minimal amountof acetonitrile, and a large amount of chloroform was added thereto torecover the oil product separated in the lower layer. Thus,(2,2,3,3,3-pentafluoropropyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl) imide (compound 8) was obtained (yield:61%).

¹H-NMR (in CD₃CN, ppm): δ 8.15 (d, J=8 Hz o-H), 7.82 (t, J=8 Hz p-H),7.61 (t, J=8 Hz m-H), 4.80 (t, J=17 Hz, CH₂)

¹⁹F-NMR (internal standard: C₆F₆, in CD₃CN, ppm): δ 84.2 (s, CF₃S), 80.4(s, CF₃), 55.7 (t, J=17 Hz, CF₂)

IR (cm⁻¹): 1201(SO₂), 1345(SO₂)

Elemental analysis: found: C, 19.89%; H, 1.24%; N, 2.07%.

calculated: C, 21.41%; H, 1.14%; N, 2.27%.

Example 9 Synthesis of 1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumbis(trifluoromethanesulfonyl)imide (Compound 9) using Compound 7

(2,2,2-Trifluoroethyl)(phenyl)iodoniumbis(trifluoromethanesulfonyl)imide (compound 7) (3.4 g, 6 mmol) andmethylene chloride (12 ml) were placed in a reaction vessel to convertthe inside of the reaction vessel to a nitrogen atmosphere. Whilestirring and cooling in an ice bath, 1-methylimidazole (0.49 g, 6 mmol)was added dropwise thereto over the course of 1 minute. After thedropwise addition thereof, the ice bath was removed, and the mixture wasallowed to react at room temperature for 3 hours. After the completionof the reaction, the solvent was removed by distillation. The resultingliquid product was washed with water and then with hexane in order toremove a side product, iodobenzene. Subsequently, this liquid productwas dissolved in a small amount of ethyl acetate, and a large amount ofether was added thereto to separate the liquid product. The liquidproduct was separated from the solvent and then dried at 110° C. underreduced pressure using a vacuum pump. Thus, pure1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumbis(trifluoromethanesulfonyl)imide (compound 9) was obtained as a liquidsubstance (yield 1.94 g, 73%). When the product is colored, it may besubjected to decolorization with active carbon. Physical property,elemental analysis and spectral data of the compound 9 are shown inTable 8.

Example 10 Synthesis of 1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumbis(trifluoromethanesulfonyl)imide (Compound 9) and p-fluoroiodobenzeneusing Compound 1

(2,2,2-Trifluoroethyl)(4-fluorophenyl)iodoniumbis(trifluoromethanesulfonyl)-imide (17.6 g, 30 mmol) and methylenechloride (60 ml) were placed in a reaction vessel to convert the insideof the reaction vessel to a nitrogen atmosphere. While stirring andcooling in an ice bath, 1-methylimidazole (2.46 g, 30 mmol) was addeddropwise thereto. After the dropwise addition thereof, the ice bath wasremoved, and the mixture was allowed to react at room temperature for 3hours. After the completion of the reaction, the solvent was removed bydistillation. The resulting liquid product was washed with hexane (orpentane), water, and then hexane (or pentane). Subsequently, this liquidproduct was dissolved in a small amount of ethyl acetate, and a largeamount of ether was added thereto to separate the liquid product. Theliquid product was separated from the solvent and then dried at 110° C.for 6 hours under reduced pressure using a vacuum pump. Thus, pure1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumbis(trifluoromethanesulfonyl)imide (compound 9) was obtained as a liquidsubstance (yield 11.5 g, 86%). When the product is colored, it may besubjected to decolorization with active carbon. Separately,p-fluoroiodobenzene was obtained from the aforementioned hexane (orpentane) wash in a substantially quantitative manner.

Example 11 Synthesis of1-methyl-3-(2′,2′,3′,3′,3′-pentafluoropropyl)imidazoliumbis(trifluoromethanesulfonyl)imide (Compound 11) and p-fluoroiodobenzeneusing Compound 3

Pure 1-methyl-3-(2′,2′,3′,3′,3′-pentafluoropropyl)imidazoliumbis-(trifluoromethanesulfonyl)imide (compound 11) was obtained as aliquid substance in the same manner as in Example 10, except thatcompound 3 was used instead of compound 1 (yield 90%). Also,p-fluoroiodobenzene was obtained in a substantially quantitative manner.Physical property, elemental analysis and spectral data of the compound11 are shown in Table 8.

Example 12 Synthesis of 1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumN-(trifluoromethanesulfonyl)trifluoroacetamide (Compound 12) by SaltExchange

A starting material, 1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumtriflate, can be synthesized as shown below.

1-Methylimidazole (0.82 g, 10 mmol) was added to methylene chloride (20ml), and (2,2,2-trifluoroethyl)(phenyl)iodonium triflate (4.54 g, 10mmol) was added thereto while stirring in an ice bath. Thereafter, themixture was stirred at room temperature for 3 hours. Methylene chloridewas removed by distillation, and the residue was then dried using avacuum pump while being heated. Thus,1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazolium triflate of interest wasobtained in a substantially quantitative manner.

1-Methyl-3-(2′,2′,2′-trifluoroethyl)imidazolium triflate (10 mmol) andwater (10 ml) were placed in a reaction vessel, and a solution of sodiumN-(trifluoromethanesulfonyl)trifluoroacetamide (2.94 g, 11 mmol) andwater (3 ml) were added thereto while stirring. The mixture was thenstirred for 15 minutes. The lower oil layer was separated, and thislayer was repeatedly washed with water. The obtained oil product wasdehydrated using a vacuum pump at 110° C. for 3 hours, and1-methyl-3-(2′,2′,2′-trifluoroethyl)imidazoliumN-(trifluoromethanesulfonyl)-trifluoroacetamide (compound 12) wasobtained (yield 2.87 g, 70%). When further purification is required, theoil product may be dissolved in a small amount of ethyl acetate, and alarge amount of ether may be added thereto to separate the oil productand the product may be dried. Alternatively, when the product iscolored, it may be treated with active carbon. Physical property,elemental analysis and spectral data of the compound 12 are shown inTable 8.

Examples 14 to 22

A variety of fluoroalkyl-substituted imidazolium salts were synthesizedin accordance with process A or process B using starting materials andreaction conditions shown in Table 1. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange).

TABLE 1 Synthesis of fluoroalkyl-substituted imidazolium salts Ex.Method Material 1 Material 2 Reaction Conditions Product Yield 14 A

CH₂Cl₂ 20 mL 0° C. → r.t., 1 h Na₂CO₃ 10 mmol

62% 15 A

CH₂Cl₂ 20 mL 0° C. → r.t., 3 h Na₂CO₃ 15 mmol

78% 16 A

CH₂Cl₂ 10 mL 0° C. → r.t., 2.2 h

78% 17 A

CH₂Cl₂ 10 mL 0° C. → r.t., 1.5 h

80% 18 A

CH₂Cl₂ 10 mL 0° C. → r.t., 1.5 h

80% 19 B

H₂O 10 mL r.t., 5 min

85% 20 B

H₂O 10 mL r.t., 20 min

89% 21 B

H₂O 10 mL r.t., 10 min

86% 22 B

H₂O 5 mL 80° C., 10 min

74%

Example 23 to 30

A variety of fluoroalkyl-substituted pyridinium salts were synthesizedin accordance with process A or process B using starting materials andreaction conditions shown in Table 2. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange).

TABLE 2 Synthesis of fluoroalkyl-substituted pyridinium salts Ex. MethodMaterial 1 Material 2 Reaction Conditions Product Yield 23 A

CH₂Cl₂ 10 mL 0° C. → r.t., 30 min

89% 24 A

CH₂Cl₂ 10 mL 0° C. → r.t., 1 h

89% 25 A

CH₂Cl₂ 10 mL 0° C. → r.t., 2.75 h

88% 26 A

CH₂Cl₂ 10 mL 0° C. → r.t., 2.75 h

64% 27 A

CH₂Cl₂ 50 mL 0° C. → r.t., 3.1 h

62% 28 A

CH₂Cl₂ 20 mL 0° C. → r.t., 3.1 h

82% 29 B

H₂O 20 mL r.t., 10 min

82% 30 B

H₂O 20 mL r.t., 10 min

86%

Examples 31 to 34

A variety of fluoroalkoxy-substituted pyridinium salts were synthesizedin accordance with process A or process B using starting materials andreaction conditions shown in Table 3. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange).

TABLE 3 Synthesis of fluoroalkyloxy-substituted pyridinium salts Ex.Method Material 1 Material 2 Reaction Conditions Product Yield 31 A

CH₂Cl₂ 50 mL 0° C. → r.t., 3 h

85% 32 A

CH₂Cl₂ 50 mL 0° C. → r.t., 3 h

84% 33 B

H₂O 10 mL r.t., 5 min

57% 34 B

H₂O 10 mL r.t., 10 min

79%

Examples 35 to 61

A variety of fluoroalkyl-substituted ammonium salts were synthesized inaccordance with process A or process B using starting materials andreaction conditions shown in Table 4. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange).

TABLE 4 Synthesis of fluoroalkyl-substituted ammonium salts Ex. MethodMaterial 1 Material 2 Reaction Conditions Product Yield 35 A (CH₃CH₂)₃N10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL r.t., 1 h

67% 36 A CH₃(CH₂)₂CH₂N(CH₂CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL r.t., 1 h

67% 37 A CH₃(CH₂)₂CH₂N(CH₃)₂ 40 mmol

CH₂Cl₂/H₂O(2/1) 120 mL r.t., 1.8 h

91% 38 B

LiN(SO₂CF₃)₂ 18.8 mol H₂O 30 mL r.t., 5 min

97% 39 A CH₃(CH₂)₄CH₂N(CH₂CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL CF₃CH₂OH 50 mmol 0° C. → r.t., 1.5 h

77% 40 A

CH₂Cl₂/H₂O(1/1) 8 mL CF₃CH₂OH 10 mmol 0° C. → r.t., 3.1 h

63% 41 A

CH₂Cl₂/H₂O(1/1) 20 mL CF₂CH₂OH 2.5 mmol 0° C. → r.t., 2.5 h

65% 42 A CH₃(CH₂)₄CH₂NHCH₃ 10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL NaHCO₃ 15 mmol r.t., 5 h

95% 43 A CH₃(CH₂)₂CH₂NHCH₃ 10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL NaHCO₃ 15 mmol 0° C. → r.t., 5 h

67% 44 B

H₂O 20 mL r.t., 10 min

76% 45 B

H₂O 20 mL r.t., 20 min

66% 46 B

CH₃OH/H₂O(11/30) 41 mL r.t., 11 min

74% 47 B

CH₃OH/H₂O(9/30) 39 mL r.t., 11 min

67% 48 A (CH₃CH₂OCH₂CH₂)₂NH 5 mmol

CH₂Cl₂/H₂O(1/1) 20 mL NaHCO₃ 6 mmol 0° C. → r.t., 14 h

81% 49 A CH₃OCH₂CH₂NHCH₂CH₃ 5 mmol

CH₂Cl₂/H₂O(1/1) 20 mL NaHCO₃ 6 mmol 0° C. → r.t., 17 h

80% 50 A CH₃CH₂OCH₂CH₂N(CH₂CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(1/2) 30 mL 0° C. → r.t., 3 h

89% 51 B

H₂O 20 mL r.t., 10 min

90% 52 A CH₃OCH₂CH₂N(CH₂CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

84% 53 B

H₂O 10 mL r.t., 15 min

72% 54 A CH₃CH₂OCH₂CH₂N(CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

78% 55 A CH₃OCH₂CH₂N(CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

77% 56 A CF₃CH₂OCH₂CH₂N(CH₂CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

84% 57 B

H₂O 10 mL r.t., 5 min

77% 58 B

H₂O 10 mL r.t., 5 min

68% 59 A CH₃CH₂OCH₂CH₂CH₂N(CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

72% 60 A CH₃OCH₂CH₂OCH₂CH₂N(CH₃)₂ 10 mmol

CH₂Cl₂/H₂O(2/1) 30 mL 0° C. → r.t., 3 h

81% 61 B

H₂O 10 mL r.t., 10 min

71%

Examples 62 to 64

A variety of fluoroalkoxy-substituted ammonium salts were synthesized inaccordance with process A or process B using starting materials andreaction conditions shown in Table 5. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange). In Examples 62, 63, and 64,(CH₃)₃N⁺CH₂CF₃ N⁻(SO₂CF₃)₂, (CH₃CH₂)₃N⁺CH₂CF₃ N⁻(SO₂CF₃)₂, andCH₃CH₂CH₂CH₂N⁺(CH₃)₂(CH₂CF₃) N⁻(SO₂CF₃)₂ were obtained as side productsat yields of 44%, 9%, and 30%, respectively.

TABLE 5 Synthesis of fluoroalkyloxy-substituted ammonium salts Ex.Method Material 1 Material 2 Reaction Conditions Product Yield 62 A

CH₂Cl₂ 20 mL 0° C. → r.t., 3.1 h

32% 63 A

CH₂Cl₂ 12 mL 0° C. → r.t., 3.1 h

57% 64 A

CH₂Cl₂ 80 mL 0° C. → r.t., 3.1 h

54%

Examples 65 to 72

A variety of fluoroalkyl-substituted sulfonium salts were synthesized inaccordance with process A or process B using starting materials andreaction conditions shown in Table 6. Process A is similar to the methodas described in Example 10, and process B is similar to the method asdescribed in Example 12 (salt exchange).

TABLE 6 Synthesis of fluoroalkyl-substituted sulfonium salts Ex. MethodMaterial 1 Material 2 Reaction Conditions Product Yield 65 A (CH₃CH₂)₂S40 mmol

CH₂Cl₂ 50 mL 0° C. → r.t., 3.1 h

89% 66 A (CH₃CH₂)₂S 5.25 mmol

CH₂Cl₂ 10 mL r.t., 3 h

94% 67 A CH₃CH₂SCH₃ 10 mmol

CH₂Cl₂ 15 mL 0° C. → r.t., 3.1 h

88% 68 A [CH₃(CH₂)₄CH₂)₂S 10 mmol

CH₂Cl₂ 50 mL 0° C. → r.t., 3.1 h

89% 69 A CH₃CH₂SH 5 mmol

CH₂Cl₂ 10 mL Na₂CO₃ 15 mmol 0° C. → r.t., 3.1 h

32% 70 A CH₃(CH₂)₄CH₂SH 10 mmol

CH₂Cl₂/H₂O(1/1) 40 mL NaHCO₃ 15 mmol 0° C. → r.t., 3.1 h

72% 71 B

H₂O 10 mL r.t., 10 min

69% 72 B

H₂O 10 mL r.t., 10 min

79%

Examples 73 to 75

A variety of fluoroalkyl-substituted oxazolium, thiazolium, andisoxazolium salts were synthesized in accordance with process A orprocess B using starting materials and reaction conditions shown inTable 7. Process A is similar to the method as described in Example 10,and process. B is similar to the method as described in Example 12 (saltexchange).

TABLE 7 Synthesis of fluoroalkyl-substituted oxazolium, isooxazolium,and thiazolium salts Ex. Method Material 1 Material 2 ReactionConditions Product Yield 73 A

CH₂Cl₂ 20 mL 0° C. → r.t., 3.1 h

37% 74 A

CH₂Cl₂ 20 mL 0° C. → r.t., 3.1 h

71% 75 A

CH₂Cl₂ 20 mL 0° C. → r.t., 22.1 h

58%

The melting points, elemental analyses, and ¹⁹F-NMR spectral data ofcompounds obtained in Examples 9 to 75 are shown in Table 8 below. Thecompounds of a melting point which is room temperature (about 25° C.) orlower showed a liquid state at room temperature. The compound of amelting point which is higher than room temperature showed or may show aliquid state at room temperature due to the supercooling phenomenon.

TABLE 8 Properties, elemental analyses, and spectral data of theproducts. ¹⁹F-NMR(in acetonitrile-d₃; standard Ex. m.p. ElementalAnalysis C₆F₆) 9, 10 <r.t. Found: C, 21.49; H, 1.85; N, 9.35 91.90(t,J=9.2Hz, CF₃), 84.23(s, SCF₃) Calcd: C, 21.58; H, 1.81; N, 9.44 11 <r.t.Found: C, 21.75; H, 1.73; N, 8.41 84.23(s, SCF₃), 79.79(s, CF₃),42.59(t, Calcd: C, 21.82; H, 1.63; N, 8.48 J=15.2Hz, CF₂) 12 <r.t.Found: C, 26.39; H, 1.96; N, 10.21 91.92(t, J=8.4Hz, 3F, CF₃), 87.89(s,3F, Calcd: C, 26.41; H, 1.97; N, 10.27 COCF₃), 84.55(s, 3F, SCF₃) 1463.7-64.9 Found: C, 21.04; H, 1.43; N, 8.17 92.23(s, 6F, CF₃), 84.29(s,6F, SCF₃) Calcd: C, 21.06; H, 1.37; N, 8.19 15 78.8-79.6 Found: C,21.60; H, 1.20; N, 6.94 84.27(s, 6F, SCF₃), 79.92(s, 6F, CF₃), Calcd: C,21.54; H, 1.15; N, 6.85 42.86(t, J=14.9Hz, 4F, CF₂) 16 48.0 Found: C,21.35; H, 1.32; N, 7.52 92.19(t, J=8.5Hz, 3F, CF₃), 84.25(s, 6F, (DSC)*Calcd: C, 21.32; H, 1.25; N, 7.46 SCF₃), 79.89(s, 3F, CF₂CF₃), 42.84(t,J=14.9Hz, 2F, CF₂) 17 27.0 Found: C, 22.19; H, 1.35; N, 7.05 84.60(s,6F, SCF₂CF₃), 79.83(s, 3F, (DSC)* Calcd: C, 22.19; H, 1.35; N, 7.06CF₃), 46.20(s, 4F, SCF₂), 42.61(t, J=15.4Hz, 2F, CF₂) 18 <r.t. Calcd: C,22.03; H, 1.48; N, 7.71 92.07(t, J=8.5Hz, 3F, CF₃), 84.77(s, 6F, Found:C, 21.99; H, 1.53; N, 7.65 CF₂CF₃), 46.32(s, 4F, CF₂) 19 <r.t. Found: C,26.22; H, 1.78; N, 9.18 91.90(t, J=8.4Hz, 3F, CF₃), 84.54(s, 3F, Calcd:C, 26.15; H, 1.76; N, 9.15 SCF₃), 81.31(s, 3F, CF₂CF₃), 43.54(s, 2F,CF₂) 20 <r.t. Found: C, 25.92; H, 1.71; N, 8.19 91.90(t, J=8.5Hz, 3F,CH₂CF₃), 84.59(s, Calcd: C, 25.94; H, 1.58; N, 8.25 3F, SCF₃), 82.86(t,J=8.6Hz, 3F, CF₃), 45.94(q, J=8.3Hz, 2F, COCF₂), 37.11(s, 2F, —COCF₂CF₂)21 <r.t. Found: C, 21.76; H, 1.69; N, 8.54 91.43(t, J=8.4Hz, 3F,CH₂CF₃), 84.66(s, Calcd: C, 21.82; H, 1.63; N, 8.48 3F, SCF₃), 83.75(s,3F, CF₂CF₃), 45.66(s, 2F, SCF₂) 22 <r.t. Found: C, 24.74; H, 1.29; N,7.29 92.16(t, J=8.5Hz, 3F, CH₂CF₃), 84.53(s, Calcd: C, 24.97; H, 1.22;N, 7.28 3F, SCF₃), 81.30(s, 3F, COCF₂CF₃), 79.88(s, 3F, CH₂CF₂CF₃),43.51(s, 2F, COCF₂), 42.86(t, J=15.5Hz, 2F, CH₂CF₂) 23 41.0-41.5 Found:C, 24.35; H, 1.63; N, 6.42 92.61(t, J=7.7Hz, CF₃), 84.25(s, SCF₃) Calcd:C, 24.44; H, 1.60; N, 6.33 24 65.2-66.5 Found: C, 24.36; H, 1.47; N,5.84 84.24(s, SCF₃), 80.15(s, CF₃), 42.87(t, Calcd: C, 24.40; H, 1.43;N, 5.69 J=15.2Hz, CF₂) 25 24.5 Found: C, 26.19; H, 2.11; N, 6.3092.68(t, J=7.5Hz, CF₃), 84.22(s, SCF₃) (DSC)* Calcd: C, 26.32; H, 1.99;N, 6.14 26 35.7 Found: C, 26.04; H, 1.88; N, 5.23 84.24(s, SCF₃),80.08(s, CF₃), 42.95(t, Calcd: C, 26.09; H, 1.79; N, 5.53 J=15.4Hz, CF₂)27 <r.t. Found: C, 28.11; H, 2.38; N, 5.93 92.73(t, J=7.9Hz, 3F, CF₃),84.30(s, 6F, Calcd: C, 28.09; H, 2.36; N, 5.96 SCF₃) 28 <r.t. Found: C,25.51; H, 2.28; N, 5.94 92.83(t, J=8.1Hz, 3F, CF₃), 84.29(s, Calcd: C,25.43; H, 1.92; N, 5.93 6F, SCF₃) 29 <r.t. Found: C, 33.31; H, 2.47; N,6.44 92.7(t, J=8.4Hz, 3F, CF₃), 87.91(s, 3F, Calcd: C, 33.19; H, 2.55;N, 6.45 COCF₃), 84.56(s, 3F, SCF₃) 30 <r.t. Found: C, 32.35; H, 2.46; N,5.85 92.71(t, J=8.6Hz, 3F, CF₃), 84.56(s, 3F, Calcd: C, 32.24; H, 2.29;N, 5.78 SCF₃), 81.32(s, 3F, CF₂CF₃), 43.57(s, 2F, CF₂) 31 <r.t. Found:C, 23.58; H, 1.59; N, 6.12 91.22(t, J=8.2Hz, 3F, CF₃), 84.32(s, 6F,Calcd: C, 23.59; H, 1.54; N, 6.11 SCF₃) 32 <r.t. Found: C, 25.45; H,1.94; N, 5.97 92.73(t, J=8.5Hz, 3F, CF₃), 84.30(s, 6F, Calcd: C, 25.43;H, 1.92; N, 5.93 SCF₃) 33 <r.t. Found: C, 28.54; H, 1.50; N, 6.6691.19(t, J=7.7Hz, 3F, CF₃), 87.93(s, 3F, Calcd: C, 28.45; H, 1.67; N,6.63 COCF₃), 84.56(s, 3F, SCF₃) 34 <r.t. Found: C, 28.00; H, 1.53; N,6.02 91.21(t, J=7.7Hz, 3F, CF₃), 84.53(s, 3F, Calcd: C, 27.98; H, 1.49;N, 5.93 SCF₃), 81.31(s, 3F, CF₂), 43.56(s, 2F, CF₂CF₃) 35 83.5-85.0Found: C, 25.89; H, 3.66; N, 6.13 101.79(t, J=8.4Hz, 3F, CF₃), 84.30(s,6F, Calcd: C, 25.86; H, 3.69; N, 6.03 SCF₃) 36 64.0-66.7 Found: C,29.01; H, 3.56; N, 5.80 101.81(t, J=8.7Hz, 3F, CF₃), 84.23(s, 6F, Calcd:C, 29.27; H, 4.30; N, 5.69 SCF₃) 37 <r.t. Found: C, 25.84; H, 3.67; N,6.08 101.38(t, J=8.9Hz, 3F, CF₃), 84.29(s, 6F, 38 Calcd: C, 25.86; H,3.69; N, 6.03 SCF₃) 39 <r.t. Found: C, 31.40; H, 5.01; N, 5.68 101.80(t,J=9.0Hz, 3F, CF₃), 84.31(s, 6F, Calcd: C, 32.31; H, 4.845; N, 5.38 SCF₃)40 65.1-66.4 Found: C, 26.06; H, 3.38; N, 6.11 102.20(t, J=8.7Hz, 3F,CF₃), 84.30(s, 6F, Calcd: C, 25.98; H, 3.27; N, 6.06 SCF₃) 41 31.1Calcd: C, 25.11; H, 3.16; N, 5.86 102.36(t, J=8.4Hz, 3F, CF₃), 84.43(s,6F, (DSC)* Found: C, 24.97; H, 3.17; N, 5.74 SCF₃) 42 <r.t. Found: C,27.93; H, 3.67; N, 5.08 102.29(t, J=7.9Hz, 3F, CF₃), 84.30(s, 6F, Calcd:C, 27.86; H, 3.60; N, 5.00 SCF₃) 43 80.8-81.9 Found: C, 25.71; H, 2.94;N, 5.34 102.31(t, J=7.6Hz, 3F, CF₃), 84.23(s, 6F, Calcd: C, 24.82; H,3.03; N, 5.26 SCF₃) 44 <r.t. Found: C, 30.90; H, 4.01; N, 6.54 101.39(t,J=8.0Hz, 3F, CF₃), 87.92(s, 3F, Calcd: C, 30.85; H, 4.00; N, 6.54COCF₃), 84.58(s, 3F, SCF₃) 45 <r.t. Found: C, 30.11; H, 3.65; N, 5.91101.38(t, J=8.9Hz, 3F, CF₃), 84.56(s, 3F, Calcd: C, 30.13; H, 3.58; N,5.86 SCF₃), 81.32(s, 3F, CF₂CF₃), 43.57(s, 2F, CF₂) 46 <r.t. Found: C,32.28; H, 3.57; N, 5.24 102.28(t, J=8.2Hz, 6F, CF₃), 87.88(s, 3F, Calcd:C, 32.07; H, 3.84; N, 5.34 COCF₃), 84.53(s, 3F, SCF₃) 47 <r.t. Found: C,31.50; H, 3.51; N, 4.92 102.28(t, J=7.8Hz, 6F, CF₃), 84.52(s, 3F, Calcd:C, 31.37; H, 3.51; N, 4.88 SCF₃), 81.30(s, 3F, CF₂), 43.53(s, 2F,CF₂CF₃) 48 63.7-65.0 Found: C, 27.76; H, 3.66; N, 4.75 103.53(t,J=8.2Hz, 6F, CF₃), 84.27(s, 6F, Calcd: C, 28.48; H, 3.76; N, 4.74 SCF₃)49 55.1-58.0 Found: C, 24.08; H, 3.06; N, 5.10 103.00(t, J=8.4Hz, 6F,CF₃), 84.27(s, 6F, Calcd: C, 24.09; H, 2.94; N, 5.11 SCF₃) 50 <r.t.Found: C, 28.30; H, 4.19; N, 5.47 102.43(t, J=9.2Hz, 3F, CF₃), 84.28(s,6F, Calcd: C, 28.35; H, 4.16; N, 5.51 SCF₃) 51 <r.t. Found: C, 29.56; H,3.48; N, 5.28 101.39(t, J=8.6Hz, 3F, CF₃), 84.57(s, 3F, Calcd: C, 29.55;H, 3.24; N, 5.30 SCF₃), 82.85(t, J=8.6Hz, 3F, CF₂CF₃), 46.96 (q,J=9.2Hz, 2F, —COCF₂), 37.10(s, 2F, CF₂CF₃) 52 <r.t. Found: C, 26.84; H,3.87; N, 5.63 102.42(t, J=8.1Hz, 3F, CF₃), 84.30(s, 6F, Calcd: C, 26.72;H, 3.87; N, 5.67 SCF₃) 53 <r.t. Found: C, 32.00; H, 4.16; N, 5.43102.43(t, J=8.9Hz, 3F, CF₃), 84.55(s, 3F, Calcd: C, 32.19; H, 4.05; N,5.36 SCF₃), 81.32(s, 3F, CF₂CF₃), 43.59(s, 2F, COCF₂) 54 <r.t. Found: C,25.02; H, 3.69; N, 5.81 101.76(t, J=8.7Hz, 3F, CF₃), 84.32(s, 6F, Calcd:C, 25.00; H, 3.57; N, 5.83 SCF₃) 55 <r.t. Found: C, 23.15; H, 3.27; N,6.02 101.75(t, J=8.9Hz, 3F, CF₃), 84.32(s, 6F, Calcd: C, 23.18; H, 3.24;N, 6.01 SCF₃) 56 <r.t. Found: C, 25.53; H, 3.26; N, 5.06 102.37(t,J=8.5Hz, 3F, CF₃), 89.38(t, J=8.8Hz, Calcd: C, 25.63; H, 3.23; N, 4.983F, —OCH₂CF₃), 84.32(s, 6F, SCF₃) 57 <r.t. Found: C, 27.52; H, 3.19; N,5.87 101.74(t, J=9.0Hz, 3F, CF₃), 84.55(s, 3F, Calcd: C, 27.51; H, 3.15;N, 5.83 SCF₃), 81.32(s, 3F, CF₂CF₃), 43.59(s, 2F, COCF₂) 58 <r.t. Found:C, 29.16; H, 3.45; N, 5.68 101.75(t, J=8.2Hz, 3F, CF₃), 84.56(s, 3F,Calcd: C, 29.16; H, 3.47; N, 5.67 SCF₃), 81.33(s, 3F, CF₂CF₃), 43.59(s,2F, COCF₂) 59 <r.t. Found: C, 26.64; H, 3.84; N, 5.73 100.77(t, J=8.3Hz,3F, CF₃), 83.63(s, 6F, Calcd: C, 26.72; H, 3.87; N, 5.67 SCF₃) 60 <r.t.Found: C, 25.87; H, 3.76; N, 5.56 101.73(t, J=8.1Hz, 3F, CF₃), 84.28(s,6F, Calcd: C, 25.89; H, 3.75; N, 5.49 SCF₃) 61 <r.t. Found: C, 29.45; H,3.60; N, 5.27 101.72(t, J=8.5Hz, 3F, CF₃), 84.53(s, 3F, Calcd: C, 29.78;H, 3.65; N, 5.34 SCF₃), 81.31(s, 3F, CF₂CF₃), 43.57(s, 2F, COCF₂) 62<r.t. Found: C, 19.34; H, 2.54; N, 6.64 100.10(t, 2.17F, J=8.6Hz,impurity), 90.62 Calcd: C, 19.18; H, 2.53; N, 6.39 (t, J=7.9Hz, 3F,CF₃), 83.64(s, 11.72F, SCF₃) 63 67.4-69.1 Found: C, 24.99; H, 3.24; N,5.98 101.78(t, 0.27F, J=8.5Hz, impurity), 91.94 Calcd: C, 25.00; H,3.57; N, 5.83 (t, 3F, J=8.4Hz, CF₃), 84.28(s, 6.81F, SCF₃) 64 <r.t.Found: C, 24.97; H, 3.61; N, 6.20 101.38(t, J=9.1Hz, 1.32F, impurity),91.47 Calcd: C, 25.00; H, 3.57; N, 5.83 (t, J=7.8Hz, 3F, CF₃), 84.30(s,11.51F, SCF₃) 65 <r.t. Found: C, 21.21; H, 2.69; N, 3.13 101.88(t,J=9.0Hz, CF₃), 84.25(s, SCF₃) Calcd: C, 21.19; H, 2.67; N, 3.09 6659.0-60.2 Found: C, 21.39; H, 2.50; N, 2.87 84.24(s, SCF₃), 79.44(s,CF₂CF₃), 51.78(t, Calcd: C, 21.47; H, 2.40; N, 2.78 J=16.7Hz, CF₂) 6731.9 Found: C, 19.18; H, 2.28; N, 3.21 102.06(t, J=8.8Hz, 3F, CF₃),84.31(s, 6F, (DSC)* Calcd: C, 19.14; H, 2.29; N, 3.19 SCF₃) 68 <r.t.Found: C, 34.00; H, 5.03; N, 2.51 101.88(t, J=9.4Hz, 3F, CF₃), 84.33(s,6F, Calcd: C, 33.98; H, 4.99; N, 2.48 SCF₃) 69 52.1-53.5 Found: C,19.10; H, 1.78; N, 2.81 102.21(t, J=8.6Hz, 3F, CF₃), 84.28(s, 6F, Calcd:C, 18.94; H, 1.79; N, 2.76 SCF₃) 70 60.2-62.4 Found: C, 24.95; H, 2.79;N, 2.55 102.16(t, J=8.5Hz, 3F, CF₃), 84.29(s, 6F, Calcd: C, 25.58; H,3.04; N, 2.49 SCF₃) 71 <r.t. Found: C, 25.90; H, 2.92; N, 3.28 101.90(t,J=9.5Hz, 3F, CF₃), 87.92(s, 3F, Calcd: C, 25.90; H, 2.90; N, 3.36COCF₃), 84.57(s, 3F, SCF₃) 72 <r.t. Found: C, 25.79; H, 2.59; N, 3.02101.88(t, J=9.4Hz, 3F, CF₃), 84.55(s, 3F, Calcd: C, 25.70; H, 2.59; N,3.00 SCF₃), 81.32(s, 3F, CF₂CF₃), 43.57(s, 2F, CF₂) 73 48.5-49.7 Found:C, 19.48; H, 1.26; N, 6.61 93.43(t, J=8.1Hz, 3F, CF₃), 84.31(s, 6F,Calcd: C, 19.45; H, 1.17; N, 6.48 SCF₃) 74 41.6-44.1 Found: C, 18.69; H,1.16; N, 6.29 92.87(t, J=8.0Hz, 3F, CF₃), 84.34(s, 6F, Calcd: C, 18.75;H, 1.12; N, 6.25 SCF₃) 75 <r.t. Found: C, 19.48; H, 1.42; N, 6.4993.91(t, J=8.0Hz, 3F, CF₃), 84.34(s, 6F, Calcd: C, 19.45; H, 1.17; N,6.48 SCF₃) r.t.: room temperature(about 25° C.) DSC: differentialscanning calorimetry *Melting point is determined by DSC.

Example 76 Measurement of Oxidation Potential and Reduction Potential byCyclic Voltammetry

Cyclic voltammogram for the following compounds were measured, and thepotential window of each compound was determined. As a comparativeexample, EMI-TFSI (1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide) was used.

Conditions for cyclic voltammetry are as follows:

-   Working electrode: Pt electrode-   Electrode couple·reference electrode: Ag-   Voltage scan rate: 50 mV/sec

The oxidation potential and the reduction potential of each compoundthat were measured by cyclic voltammetry are shown in the table below.

TABLE 9 Comparative Example I-1 A-1 S-1 EMI-TFSI Oxidation potential 5.85.8 5.9 5.9 (V vs Li) Reduction potential 1.4 0.5 1.2 1.5 (V vs Li)Difference between 4.4 5.3 4.7 4.4 oxidation potential and reductionpotential

As shown in Table 9, the compound of the present invention has apotential window (a difference between the oxidation potential and thereduction potential) equivalent to or wider than that of conventionalambient-temperature molten salts.

Example 77 Ion Conductivity

Ion conductivities of the following compounds I-1(compound of Ex.12) andTFEMI-TFSI(comparative compound) were measured. The results are shown inFIG. 1.

As is apparent from FIG. 1, ion conductivity of ambient-temperaturemolten salt I-1 is enhanced in a high temperature region compared withTFEMI-TFSI.

All publications cited herein are incorporated herein by reference intheir entirety.

INDUSTRIAL APPLICABILITY

According to the present invention, with the use of the compound offormula (VII) or (IX), fluoroalkyl and imide anion can be simultaneouslyintroduced to a heteroatom-containing compound such as imidazole,thereby easily obtaining ambient-temperature molten salts. Since theambient-temperature molten salts of the present invention have widepotential windows, excellent stability and high ion conductivities, theyare useful for electrolytes for lithium cells or the like.

1. Ambient-temperature molten salts of formula (I):

wherein Y⁺ is a pyrimidium ion of formula (IV):

wherein R1, R3, R4, and R5 are hydrogen and R2 is selected from C₁₋₂alkyl and —OCH₃, and R⁶ is —CH₂CF₃, —CH₂CF₂CF₃, or —OCH₂CF₃; Rf² is—CF₃, and Rf³ is C₁₋₂ perfluoroalkyl; and X is —SO₂— or —CO—.
 2. Theambient-temperature molten salts of claim 1 wherein X is —SO₂—.
 3. Theambient-temperature molten salts of claim 1 wherein X is —CO—.
 4. Amethod for producing a compound of formula (I):

wherein Y⁺ is a pyrimidium ion of formula (IV):

wherein R1, R3, R4, and R5 are hydrogen and R2 is selected from C₁₋₂alkyl and —OCH₃, and R⁶ is CH₂CF₃, —CH₂CF₂CF₃, or —OCH₂CF₃; Rf² is —CF₃,and Rf³ is C₁₋₂ perfluoroalkyl; and X is —SO₂—; which comprises reactinga heteroatom-containing compound selected from pyridine, pyridineN-oxide, which may be optionally substituted with C₁₋₂ alkyl, C₁₋₂ alkylhaving ether linkage, —CH₂Rf¹, or —OCH₂Rf¹, wherein Rf¹ is C₁₋₂perfluoralkyl, with a compound of formula (IX):

wherein Ar is an unsubstituted phenyl or phenyl that may be optionallysubstituted with halogen atom or C₁₋₂ alkyl, to give a compound offormula (I).
 5. The method according to claim 4, wherein Ar is phenyl orrepresented by the following formula:


6. The method according to claim 5, wherein Ar is represented by thefollowing formula: